Amazing Spider-Man #20 - 1/65

1st Scorpion, 1st Dr. Farley Stillwell. Spider-Man battles the Scorpion for the first time.



Untold Tales Of Spider-Man #23 - 8/97

1st Super Squad. Spider-Man battles the Super Squad. Crimemaster makes his first chronological appearance.



Untold Tales Of Spider-Man Annual '97 - 1997

1st Sundown. Spider-Man, along with the Fantastic Four, the Avengers, Doctor Strange, Hulk, Daredevil, X-Men, and the Submariner, battle Sundown.



Amazing Spider-Man #21 - 2/65

Spider-Man battles the Beetle for the first time with some help from the Human Torch.

Amazing Spider-Man #8 - 1/64 (2nd Story)

Spider-Man crashes the Human Torches party and tangles with the Fantastic Four.

Fantastic Four #35 - 2/65

Peter Parker makes a cameo appearance on a campus while the Fantastic Four deal with Dragon Man in his first appearance.



Untold Tales Of Spider-Man Annual '96 - 1996

Spider-Man & the Fantastic Four battle the Submariner.



Amazing Spider-Man #22 - 3/65

1st Princess Python. Spider-Man takes on the Ringmaster and his Circus of Crime which includes Princess Python.



Fantastic Four #36 - 3/65

Spider-Man "borrows" a slice of cake through the window of the Fantastic Four's headquarters.

Untold Tales Of Spider-Man #24 - 9/97

Spider-Man helps out Batwing in trying to cure himself.



Amazing Spider-Man #23 - 4/65

1st Lucky Lobo. Spider-Man battles the Green Goblin and Lucky Lobo.

Untold Tales Of Spider-Man #25 - 10/97

Spider-Man battles the Green Goblin. Relationship between the Green Goblin and Crimemaster revealed.



Amazing Spider-Man #24 - 5/65

Spider-Man sees a psychiatrist named Dr. Ludwig Rinehart and later discovers that he Mysterio in disguise.



Amazing Spider-Man #25 - 6/65

1st Spencer Smythe, 1st Spider Slayer. Spider-Man battles the first Spider Slayer. He will face many more in the future.



Amazing Spider-Man #26 - 7/65

1st Crimemaster, 1st Patch (Frederick Foswell). Spider-Man battles the Crimemaster and the Green Goblin.



Amazing Spider-Man #27 - 8/65

Death Crimemaster. Spider-Man battles the Crimemaster and the Green Goblin. Crimemaster turns out to be a regular criminal.



Amazing Spider-Man #28 - 9/65

1st Molten Man. Spider-Man battles the Molten Man for the first time. Peter Parker graduates from High School.

Amazing Spider-Man Annual #2 - 1965

1st Xandu. Spider-Man battles Xandu with some help from Doctor Strange.

   
Amazing Spider-Man #29 - 10/65

Spider-Man battles the Scorpion for the second time.

 

 
Amazing Spider-Man #30 - 11/65

1st Cat Burglar. Spider-Man battles the Cat Burglar the first time. The Cat Burglar would go on to become Prowler II years later.

  Amazing Spider-Man #31 - 12/65

1st Gwen Stacy, 1st Harry Osborn, 1st Professor Miles Warren. Spider-Man battles the Master Planner's (Doctor Octopus) Henchmen. Peter Parker arrives in college (Empire State University).

 

 
 
Fantastic Four Annual #3 - 1965

Spider-Man, and many other heroes makes a minor appearance as Mister Fantastic and the Invisible Girl get married. May villains also appear trying to ruin the wedding, that include Electro and many others.